Ionic polymers and their use as wet-adhesives and coatings

ABSTRACT

The present application discloses an adhesive composition comprising a polymer of the formulae A, B and C: 
     
       
         
         
             
             
         
       
     
     and methods for using the adhesive composition. 
     
       
         
         
             
             
         
       
         
         
           
             wherein x and y define the block polymer and are integer greater than 1.

RELATED APPLICATIONS

The present application claims priority to U.S. Provisional ApplicationNo. 62/349,328 filed Jun. 13, 2016, and U.S. Provisional Application No.62/363,605 filed Jul. 18, 2016, the contents of which are incorporatedherein by reference.

BACKGROUND

Phase transitions of aqueous solutions of charged polymers and proteinshave been reported. See Wei, W.; Waite, J. H. et al., A mussel-derivedone component adhesive coacervate. Acta Biomater 2014, 10 (4),1663-1670; Ahn, B. K.; Das; Lipshutz, B. H.; Israelachvili, J. N.;Waite, J. H. et al., High-performance mussel-inspired adhesives ofreduced complexity. Nat Commun, 2015, 6; J. N.; Waite, J. H.; Ahn, B. K.et al., Microphase Behavior and Enhanced Wet-Cohesion of SyntheticCopolyampholytes Inspired by a Mussel Foot Protein. J Am Chem Soc, 2015,137 (29), 9214-9217; Brangwynne, C. P. et al., Polymer physics ofintracellular phase transitions. Nat Phys, 2015, 11 (11), 899-904.Cation-π interaction is strong in aqueous media and may be used forwet-adhesion in biology. See Lu, Q., et al., Adhesion of mussel footproteins to different substrate surfaces. Journal of the Royal SocietyInterface, 2013, 10 (79).

SUMMARY OF THE INVENTION

In one aspect of the present application, there is disclosedcompositions and methods for generating glue, coating or adhesive, suchas wet-glue or wet-tack coating, to bind or to coat materials. As usedherein, wet-tack refers to the tackiness of a composition, a material oran adhesive in a wet environment. In another aspect, the adhesion may bebased, in part, on ionic interactions, such as cation-t interaction.

In one embodiment, the present application discloses an adhesivecomposition comprising a polymer of the formulae A, B and C:

wherein: each m, n and o is independently 100 to 1,000,000;

each a, b, s, t, x and y is independently 0, 1 or 2;

each L¹, L², L³, L⁴, L⁵ and L⁶ is independently absent or is selectedfrom the group consisting of —CH₂—, —O—, —S—, —(CH₂)₁₋₂—, —CH(CH₂—)₂—,—C(O)O—, —C(O)OCH₂—, —CH₂C(O)O—, —CH₂C(O)NH—, —C(O)NHCH₂—, —C(O)NH— and—NR′— where R′ is selected from H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅ orsubstituted benzyl, or a bond;

-   -   each A, B, M, N, X and Y is independently absent or selected        from the group consisting of an aryl, substituted aryl, aryl        ammonium, heteroaryl, substituted heteroaryl, heteroarylammonium        X⁻ and substituted heteroarylammonium X⁻, wherein each X⁻ is        independently a counter anion selected from Cl⁻, Br⁻, I⁻, —SO₄        ⁻² and —PO₄ ⁻³;

provided that not all of L¹, L², L³, L⁴, L⁵ and L⁶, and A, B, M, N, Xand Y are absent;

provided that for Formula A, only one of A, B is a heteroarylammonium X⁻or a substituted heteroarylammonium X⁻; and provided that when L¹ is—(CH₂)₁₋₂— or a bond, then the group -(A)_(a)-L²-(B)_(b) is not a groupselected from -heteroarylammonium (X⁻)-L²-dihydroxy-phenyl, asubstituted or unsubstituted imidazole and a substituted orunsubstituted imidazolinium (X⁻); or arylammonium(X⁻)-L²-dihydroxy-phenyl, a substituted or unsubstituted amine or asubstituted ammonium (X⁻) group. In one variation, at least one, two orthree of L¹, L², L³, L⁴, L⁵ and L⁶, and A, B, M, N, X and Y are present.As used herein, an asymmetric linker (e.g., L¹, L² etc) or groupdesignated as “—C(O)O—” for example, represents both the divalent groups“—C(O)O—” and “—OC(O)—” that may be inverted and may attach or link inboth directions.

In one variation of the adhesive, the molar ratio of the monomer in thepolymer or copolymer is 1:0, 1:1, or 1:1:1. In another variation of thecompound or adhesive, the ratio of m:n is 1:0 or 1:1; and the ratio ofm:n:y is 1:1:1. In another variation, m+n=100 mol %; m: 100-0 mol %; n:0-100 mol %. In another variation, m+n+y=100 mol %; m: 100-0, n: 0-100and z: 0-100.

In one variation of the above adhesive, the adhesive is formulated inwater. In another variation of the above, -(A)_(a)- is not a groupselected from an ammonium, imidazolium or pyridinium group. In anothervariation, -(A)_(a)- is a group selected from quinolinium,isoquinolinium, phenathridinium, phenanthrolinium, pyrimidinium,benzothiazolinium, benzimidazolium, benzothiadiazolinium, purinium,pyrazinium or acridinium. In another variation of the above, the polymeris prepared from a monomer; and is not a co-polymer. In one variation,at least one of the -A- and —B— groups is a curable group. In anothervariation, at least one of A, B, N and Y is a curable group.

In one aspect, there is provided an adhesive composition comprising acurable side chain of the formulae A′, B′ and C′:

wherein the polymer is further curable.

It is noted that the above depiction of the copolymers, designated asthe -L¹-(A)_(a)-L²-(B)_(b) monomer and the -L³-(M)_(m)-L⁴-(N)_(n)monomer, the designation is used only to distinguish the structures andfunctional groups of the linkers and functional groups, and is notintended to show any particular sequence of the copolymers. Thecopolymers may be random, alternating, statistical, periodic and blockcopolymers. In one variation, at least one of the -A-, —B—,-M, —N, —Xand —Y group is a curable group.

In one variation of the above, at least one of -(A)_(a)-, -(M)_(m)- and—(X)_(x)— is not a group selected from an ammonium, imidazolium andpyridinium. In another variation, at least one of -(A)_(a)-, -(M)_(m)-and —(X)_(x)— is independently selected from the group consisting ofquinolinium, isoquinolinium, phenathridinium, phenanthrolinium,pyrimidinium, benzothiazolinium, benzimidazolium, benzothiadiazolinium,purinium, pyrazinium or acridinium. In another variation, the polymer isprepared from a monomer; and is not a copolymer. In one variation, atleast one of the -A- and —B— group is a curable group. In anothervariation, at least one of B, N or Y is a curable group.

In one variation of the polymers of the present disclosure, the polymeris not associated with or coordinated with a metal ion. In anothervariation, the polymer lacks a ligand or functional group that iscapable of forming a coordinating complex with metal ions. In onevariation of the compound of the formulae A and B, at least one of thegroup A, B and X is not phenyl. In another variation, at least one ofthe group A, B and X is not derived from styrene, methyl acrylate, butylacrylate, benzyl acrylate or a styrene substituted by one —CH₂OH.

In another embodiment, there is provided an adhesive compositioncomprising a polymer of the formula:

In one aspect of the above, each A, B, M, N, X and Y is independentlyselected from the group consisting of:

wherein:

each L¹, L², L³, L⁴, L⁵ and L⁶ is independently H, —CH₃, —CH₂—, —O—,—S—, —(CH₂)₁₋₂—, —CH(CH₂—)₂—, —C(O)O—, —C(O)OCH₂—, —CH₂C(O)O—,—CH₂C(O)NH—, —C(O)NHCH₂—, —C(O)NH— and —NR′— where R′ is selected fromH, —CH₃, —CH₂CH₃ and —CH₂C₆H₅, a bond and —NR′— where R′ is selectedfrom H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅ or substituted benzyl;

each R, R¹ and R² is independently H or is selected from the groupconsisting of F, Cl, Br, I, —OH, —SiH₂OH, —NO₂, —CH₃, —CF₃, asubstituted aryl group, —CO₂H, —SO₄H, —SO₃H, —PO₄H₂, —PO₃H₂, —NH₃ ⁺,—CH₂C₆H₅, -3,4-dihydroxyphenyl, —CH₂-3,4-dihydroxyphenyl,N-succinimidyl, —NR′R″ where R′ and R″ are each independently selectedfrom H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅, and a curable group;

each R³ is independently H or is selected from the group consisting of—CH₃, —CH₂CH₃, a substituted aryl group, —CO₂H, —SO₄H, —SO₃H, —PO₄H₂,—PO₃H₂, —NH₃ ⁺ and —CH₂C₆H₅, and a curable group; and Z is —(CH₂)_(t)—or —(NH)— where t is 0 or 1.

In another aspect of the above, each of B, N and Y independentlycomprises an aldehyde derivative, an amine, glycidyl, acrylyl,methacrylyl or a vinyl derivative of the formulae:

In another aspect of the above polymer, at least one of A, B, M, N, Xand Y is independently selected from the group consisting of theformulae:

-L¹-COOH, -L¹-SO₄H, -L¹-SO₃H, -L¹-PO₄H₂, -L¹-PO₃H₂ and L¹-NH₃ ⁺;

-L³-COOH, -L³-SO₄H, -L³-SO₃H, -L³-PO₄H₂, -L³-PO₃H₂ and L³-NH₃ ⁺; and

-L⁵-COOH, -L⁵-SO₄H, -L⁵-SO₃H, -L⁵-PO₄H₂, -L⁵-PO₃H₂ and L⁵-NH₃ ⁺;

wherein each L¹, L³ and L⁵ is independently selected from a bond, —CH₂—,—O—, —S— and —NR′— where R′ is selected from H, —CH₃, —CH₂CH₃ and—CH₂C₆H₅ or substituted benzyl.

In another aspect of the above polymer, each of B, N and Y isindependently selected from the group consisting of the formulae:

In another aspect of the polymer, at least one of A, M and X isindependently selected from the group consisting of the formulae:

In yet another aspect, B, N and Y are each independently a substitutedaryl group. In another aspect of the above, each R, R¹, R² and R³ isindependently a substituted aryl group.

In another aspect of the above polymer, the substituted aryl group isselected from the group consisting of:

and b, n and y is 1 or 2.

In one variation of the adhesive, each B, N and Y is independentlyselected from the group consisting of phenyl, 2,3-dihydroxyphenyl,2,3,4-trihydroxyphenyl, 3,4,5-trihydroxyphenyl,2,3,4,5-tetrahydroxyphenyl, 2,3,4,5,6-pentahydroxyphenyl,2,3-dicarboxyphenyl, 2,3,4-tricarboxyphenyl, 3,4,5-tricarboxylphenyl,2,3,4,5-tetracarboxyphenyl, 2,3,4,5,6-pentacarboxyphenyl,2,3-disiloxyphenyl, 2,3,4-trisiloxyphenyl, 3,4,5-trisiloxyphenyl,2,3,4,5-tetrasiloxyphenyl and 2,3,4,5,6-pentasiloxyphenyl.

In another aspect, the adhesive comprises the formulae B¹, B², B³, B⁴,B⁵ and B⁶

wherein: each m and n is independently 100 to 1,000,000;

each L¹ and L³ is independently selected from a bond, —CH₂—, —O—, —S—,—C(O)O—, —C(O)OCH₂—, —CH₂C(O)O—, —CH₂C(O)NH—, —C(O)NHCH₂—, —C(O)NH— and—NR′— where R′ is selected from H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅ orsubstituted benzyl;

each R and R¹ is independently H or is selected from the groupconsisting of F, Cl, Br, I, —CF₃, —OH, —SiH₂OH, —NO₂, —CH₃, —CO₂H,—SO₄H, —SO₃H, —PO₄H₂, —PO₃H₂, —NH₃ ⁺, —CH₂C₆H₅, -3,4-dihydroxyphenyl,—CH₂-3,4-dihydroxyphenyl, —NR′R″ where R′ and R″ are each independentlyselected from H, —CH₃, —CH₂CH₃, —CH₂C₆H₅ or substituted benzyl, and acurable group;

each R³ is independently H or is selected from the group consisting of—CH₃, —CH₂CH₃, —CO₂H, —SO₄H, —SO₃H, —PO₄H₂, —PO₃H₂, —NH₃ ⁺, —CH₂C₆H₅ anda curable group; and each X⁻ is independently a counter anion selectedfrom the group Cl⁻, Br⁻, I⁻, —SO₄ ⁻² and —PO₄ ⁻³.

As depicted in this application, a group represented by the structureB³, for example,

where the substituent —R is attached between 2 carbon atoms on thepyridinium ring means that —R may be attached at any available positionon the pyridinium ring, such as the 3-, 4-, 5- or -6 position.

In another aspect, the adhesive comprises the formulae C¹, C², C³, C⁴,C⁵ and C⁶:

wherein each m, n and y is independently 100 to 1,000,000;

each L¹, L³ and L⁵ is independently selected from —CH₂—, —O—, —S—,—(CH₂)₁₋₂—, —CH(CH₂-)₂, —C(O)O—, —C(O)OCH₂—, —CH₂C(O)O—, —CH₂C(O)NH—,—C(O)NHCH₂—, —C(O)NH— and —NR′— where R′ is selected from H, —CH₃,—CH₂CH₃ and —CH₂C₆H₅ or substituted benzyl, or a bond;

each R and R¹ is independently H or is selected from the groupconsisting of F, Cl, Br, I, —OH, —SiH₂OH, —NO₂, —CH₃, —CO₂H, —SO₄H,—SO₃H, —PO₄H₂, —PO₃H₂, —NH₃ ⁺, —CH₂C₆H₅, -3,4-dihydroxyphenyl,—CH₂-3,4-dihydroxyphenyl and —NR′R″ where R′ and R″ are eachindependently selected from H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅ or substitutedbenzyl;

each R³ is independently H or is selected from the group consisting of—CH₃, —CH₂CH₃, —CO₂H, —SO₄H, —SO₃H, —PO₄H₂, —PO₃H₂, —NH₃ ⁺ and —CH₂C₆H₅;and each X⁻ is independently a counter anion selected from the groupconsisting of Cl⁻, Br⁻, I⁻, —SO₄ ⁻² and —PO₄ ⁻³.

In another aspect of the above adhesive, B, N and Y are eachindependently a substituted aryl group. In another aspect of the aboveadhesive, the substituted aryl group is selected from the groupconsisting of:

and b, n and y is 1 or 2.

In one variation of the above compounds, R, R¹, R² and R³ are not H. Inone variation of the above, b is 0. In another variation, n is 0. Inanother variation, b and n are both 0. In another variation, b is 1 andn is 0. In another variation, b is 1 and n is 1. In another variation;

In another aspect of the adhesive, the curable group is a photocurablegroup, a photopolymerizable group, a thermal curable group and a solventcurable group. In one aspect of the photocurable group, the group may becured through UV radiation, or by the use of dye-based photoinitiatorsystems using UV or visible light, thermally induced curing or solventbased curing methods. The photoinitiation may be performed using freeradical method or by ionic method. In one variation, the photoinitiatormay include doping the polymer, such as the polymer applied to thesurface(s) with a small amount of photoinitiator, followed by selectiveradiation of light, that results in a highly cross-linkedpolymer-adhesive.

In one variation, the curing adhesive with a curable group, is anepoxide (or a glycidyl group or oxirane group), polyepoxide or epoxyresin that are reactive prepolymers and polymers comprising an epoxidegroup. Epoxy groups or epoxy resins may be reacted or cross-linkedeither with themselves by way of catalytic homopolymerization, or withother co-reactants such as amines, polyfunctional amines, acids, acidanhydrides, phenols, alcohols and thiols.

In one variation, the curable group is selected from the groupconsisting of epoxides, cyanate esters and acrylamido-2-methylpropanesulfonic acid (AMPS) derivative (such as 2-acrylamido-2-methylpropanesulfonic acid). In another variation, the free radical curable groupcomprises a monomeric organofunctional silanes for polymerization maycomprise acrylatoalkylalkoxysilanes, methacrylatoalkylalkoxysilanes orvinyl alkoxysilane monomers, including3-methacryloxypropyltri-iso-propoxysilane,3-methacryloxypropyltri-iso-butoxysilane,3-methacryloxypropyltrioctoxysilane, vinyl tri-iso-butoxysilane, vinyltri-n-decoxysilane and vinyl tri-tert-butoxysilane, maleate functionalsilanes and 3-mercaptopropyl tri-iso-butoxysilane. In another variation,the radical curable group is a monomeric organofunctional silane, suchas 3-aminopropyltri-iso-propoxy silane,N-(2-aminoethyl)-3-aminopropyidi-iso-butoxy silane, 4-mercaptobutyldimethyloctyloxysilane, 3-isocyanatopropyltri-sec-butoxysilane and3-glycidoxypropylmethyl dipentoxysilane. Other curable polymers orcurable groups include polyurethanes, epoxies, polyesters, vinyl esters,polyureas and polyamides. See, for example, U.S. Pat. No. 6,069,200.

In another embodiment, the present application discloses a method forsealing a first object having a surface to a second object havingsurface in a moist or wet environment, the method comprising:

1) applying an adhesive to the surface of the first object;

2) contacting the surface of the first object comprising the adhesivewith the surface of the second object for a sufficient period of timeuntil the first and second object forms a seal;

wherein the adhesive is an adhesive composition comprising a polymer ofthe formula A, B or C:

wherein: each m, n and o is independently 100 to 1,000,000;

each a, b, s, t, x and y is independently 0, 1 or 2;

each L¹, L², L³, L⁴, L⁵ and L⁶ is independently absent or isindependently selected from —CH₂—, —O—, —S—, —(CH₂)₁₋₂—, —CH(CH₂—)₂,—C(O)O—, —C(O)OCH₂—, —CH₂C(O)O—, —CH₂C(O)NH—, —C(O)NHCH₂—, —C(O)NH— and—NR′— where R′ is selected from H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅ orsubstituted benzyl, or a bond;

each A, B, M, N, X and Y is independently absent or is independentlyselected from the group consisting of an aryl, substituted aryl,heteroaryl, substituted heteroaryl, heteroarylammonium X⁻ andsubstituted heteroarylammonium X⁻, wherein each X⁻ is independently acounter anion selected from Cl⁻, Br⁻, I⁻, —SO₄ ⁻² and —PO₄ ⁻³; providedthat not all of L¹, L², L³, L⁴, L⁵ and L⁶ and A, B, M, N, X and Y areabsent. In one variation of the above method, it is provided that forFormula A, only one of A, B is a heteroarylammonium X⁻ or a substitutedheteroarylammonium X⁻; and provided that when L¹ is —(CH₂)₁₋₂— or abond, then the group -(A)_(a)-L²-(B)_(b) is not a group selected from-heteroarylammonium (X⁻)-L²-dihydroxy-phenyl, a substituted orunsubstituted imidazole and a substituted or unsubstituted imidazolinium(X⁻).

In one variation of the method, the adhesive is a compound or a polymeras disclosed herein. In another aspect of the method, the adhesivecomprises of the formulae A¹, A², A³, A⁴, A⁵, A⁶, A⁷, A⁸, A⁹, A¹⁰, A¹¹and A¹²:

wherein: each n is independently 100 to 1,000,000;

each L¹ and L³ is independently selected from a bond, —CH₂—, —O—, —S—,—C(O)O—, —C(O)OCH₂—, —CH₂C(O)O—, —CH₂C(O)NH—, —C(O)NHCH₂—, —C(O)NH— and—NR′— where R′ is selected from H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅ orsubstituted benzyl;

each R and R¹ is independently H or is selected from the groupconsisting of F, Cl, Br, I, —OH, —SiH₂OH, —NO₂, —CH₃, —CO₂H, —SO₄H,—SO₃H, —PO₄H₂, —PO₃H₂, —NH₃ ⁺, —CH₂C₆H₅, -3,4-dihydroxyphenyl, a curablegroup, —CH₂-3,4-dihydroxyphenyl, —NR′R″ where R′ and R″ are eachindependently selected from H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅ or substitutedbenzyl;

each R³ is independently H or is selected from the group consisting of—CH₃, —CH₂CH₃, a curable group and —CH₂C₆H₅ where the C₆H₅ group isoptionally substituted with 1 substituent selected from the groupconsisting of halogen (—F, —Cl, —Br— or —I), —OH, —SH, —SiH₂OH, —NH₂,—NO₂, —CO₂H, —SO₄H, —SO₃H, —PO₄H₂, —PO₃H₂, —NH₃ ⁺, —CH₃, —CF₃, —OCH₃ and—OCF₃; and each X⁻ is independently a counter anion selected from Cl⁻,Br⁻, I⁻, —SO₄ ⁻², —PO₄ ⁻³ and CH₃CO₂ ⁻.

In one aspect of the method, the adhesive comprises of the formulae B¹,B², B³, B⁴, B⁵ and B⁶:

wherein: each m and n is independently 100 to 1,000,000;

each L¹ and L³ is independently selected from a bond, —CH₂—, —O—, —S—,—C(O)O—, —C(O)OCH₂—, —CH₂C(O)O—, —CH₂C(O)NH—, —C(O)NHCH₂—, —C(O)NH— and—NR′— where R′ is selected from H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅ orsubstituted benzyl;

each R and R¹ is independently H or is selected from the groupconsisting of F, Cl, Br, I, —OH, —SiH₂OH, —NO₂, —CO₂H, —SO₄H, —SO₃H,—PO₄H₂, —PO₃H₂, —NH₃ ⁺, —CH₃, —CH₂C₆H₅, -3,4-dihydroxyphenyl,—CH₂-3,4-dihydroxyphenyl, a curable group, —NR′R″ where R′ and R″ areeach independently selected from H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅ orsubstituted benzyl;

each R³ is independently H or is selected from the group consisting of—CO₂H, —SO₄H, —SO₃H, —PO₄H₂, —PO₃H₂, —NH₃ ⁺, —CH₃, —CH₂CH₃, —CH₂C₆H₅ orsubstituted benzyl, and a curable group; and each X⁻ is independently acounter anion selected from Cl⁻, Br⁻, I⁻, —SO₄ ⁻², —PO₄ ⁻³ and CH₃CO₂—.

In another aspect of the method, the adhesive comprises the formulae C¹,C², C³, C⁴, C⁵ and C⁶:

wherein: each m, n and o is independently 100 to 1,000,000;

each L¹, L³ and L⁵ is independently selected from a bond, —CH₂—, —O—,—S—, —C(O)O—, —C(O)OCH₂—, —CH₂C(O)O—, —CH₂C(O)NH—, —C(O)NHCH₂—, —C(O)NH—and —NR′— where R′ is selected from H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅ orsubstituted benzyl;

each R and R¹ is independently H or is selected from the groupconsisting of F, Cl, Br, I, —OH, —SiH₂OH, —NO₂, —CO₂H, —SO₄H, —SO₃H,—PO₄H₂, —PO₃H₂, —NH₃ ⁺, —CH₃, —CH₂C₆H₅, -3,4-dihydroxyphenyl, a curablegroup, —CH₂-3,4-dihydroxyphenyl, —NR′R″ where R′ and R″ are eachindependently selected from H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅ or substitutedbenzyl;

each R³ is independently H or is selected from the group consisting of—CO₂H, —SO₄H, —HSO₄ ⁻, —SO₃H, —PO₄H₂, —PO₃H₂, —NH₃ ⁺, —CH₃, —CH₂CH₃,—CH₂C₆H₅ or substituted benzyl, or a curable group; and each X⁻ isindependently a counter anion selected from Cl⁻, Br⁻, I⁻, —SO₄ ⁻² and—PO₄ ³.

In another aspect of the method, B, N and Y are each independently anaryl or substituted aryl group. In another aspect of the above method,R, R¹, R² and R³ is independently hydrogen or an aryl or substitutedaryl group. In another aspect of the method, at least one of A, B, M, N,X and Y is independently selected from the group consisting of theformulae:

-L¹-COOH, -L¹-SO₄H, -L¹-SO₃H, -L¹-PO₄H₂, -L¹-PO₃H₂ and L¹-NH₃ ⁺;

-L³-COOH, -L³-SO₄H, -L³-SO₃H, -L³-PO₄H₂, -L³-PO₃H₂ and L³-NH₃ ⁺; and

-L⁵-COOH, -L⁵-SO₄H, -L⁵-SO₃H, -L⁵-PO₄H₂, -L⁵-PO₃H₂ and L⁵-NH₃ ⁺;

wherein each L¹, L³ and L⁵ is independently selected from a bond, —CH₂—,—O—, —S— and —NR′— where R′ is selected from H, —CH₃, —CH₂CH₃ and—CH₂C₆H₅.

In another aspect of the method, each of B, N and Y independentlycomprises an amine, glycidyl, acrylyl, methacrylyl, or a vinylderivative of the formulae:

In another aspect of the method, each of B, N and Y is independentlyselected from the group consisting of the formulae:

In yet another aspect of the method, at least one of A, M and X isindependently selected from the group consisting of the formulae:

In yet another aspect of the above method, the adhesive is furthercured. In one variation of the method for sealing a first object havinga surface to a second object having surface in a moist or wetenvironment, the method comprising polymerizing a first monomer to forma polymer, such as a homopolymer, applying the polymer to the surface ofthe first object and contact the surface of a second object to thesurface of the first object comprising the polymer for a sufficientperiod of time to seal the first object to the second object. In onevariation of the method, the sealing of the first object to the secondobject is performed in a moist environment. In one variation of themethod, the most environment is an aqueous environment. In anothervariation of the method, the sealing of the first object to the secondobject is performed in water, in a moist or a wet atmosphere or underwater.

In another variation of the method, the adhesive is further cured understandard methods known in the art, such as by heat, light (UV orvisible), radiation, electron beams or by adding certain chemicaladditives. In one variation, the additive may be activated with UVradiation resulting in a UV curing process.

In another aspect of the method, the first object is independentlyselected from the group consisting of a dermis, skin, tissue, metal, ametal oxide, a mineral, mica, silicon, glass, calcium, enamel, bone,steel, tooth enamel, tooth dentin, hydroxylapatite, kaolin and zirconia;and the second object is selected from the group consisting of a dermis,skin, tissue, metal, a metal oxide, a mineral, mica, silicon, glass,calcium, enamel, bone, steel, tooth enamel, tooth dentin,hydroxylapatite, kaolin and zirconia. In another aspect, the firstobject and the second object are both dermis tissues or skin. In yetanother aspect, the first object is a tissue or dermis and the secondobject is selected from the group consisting of a metal, a metal oxide,a mineral, mica, silicon, glass, calcium, enamel, bone, steel, toothenamel, tooth dentin, hydroxylapatite, kaolin and zirconia.

In another aspect of the method, the adhesive process is performed inwater. In yet another aspect, the method further comprises the additionof saline or salt, or mixture of salts, to increase the salinity. Inanother aspect of the method, the metal, metal oxide or oxide isselected from the group consisting of silicate mineral, silica, kaolin,zirconia, aluminum, copper, chrome, chrome-cobalt, titanium, zinc, tin,indium-tin and calcium oxide. In another aspect, the method provides areusable or reversible low tack pressure sensitive adhesive or low tackadhesive or anti-slippery coating, where the process comprises: (1)dissolving the above noted adhesive in water to form an aqueous solutionof the adhesive; (2) diluting the aqueous solution of the adhesive withan alcohol, such as ethanol; (3) adding saturated NaCl aqueous solutionto the aqueous ethanolic solution; (4) spraying, applying or coating theaqueous ethanolic solution on a substrate or surface and drying thesolution such as by air drying.

In another embodiment, the adhesive is contacted with the surface andemployed after polymerization, or the adhesive is further cured, asshown in Schemes A, B and C.

DETAILED DESCRIPTION OF THE INVENTION Definition

The term “copolymer” means a polymer that is made from two or moredifferent monomers. Examples of such monomers may include ethylene,styrene and acrylonitrile, and their substituted derivatives. Forexample, two different monomers may be allowed to polymerize in areaction medium such that a copolymer is formed that contains bothresidues of the two different monomeric units. In one aspect, thecopolymer may be a random copolymer having no definitive sequence of themonomer units. In another aspect, the copolymer may be a regularcopolymer with regular alternating sequence of two monomer units. Inanother aspect, the copolymer may be a block copolymer containing ablock of one monomer connected to a block of another monomer.

The total number average molecular weight (Mn, or Mn) of the polymers orblock polymers or copolymers of the present invention is typicallyprovided in various ranges, of from about 5,000 to 6,000, 6,000 to8,000, 8,000 to 10,000, 10,000 to 12,000, 28,000 to 30,000, 43,000 to45,000, 53,000 to 55,000, 58,000 to 60,000, 78,000 to 80,000, 88,000 to90,000, 97,000 to 100,000, 115,000 to 120,000, 125,000 to 130,000,135,000 to 140,000, 145,000 to 150,000, 200,000 to 400,000, 400,000 to500,000, 500,000 to 600,000, 600,000 to 700,000 or about 700,000 toabout 1,000,000. The Mn may be determined standard methods employed inthe art, such as by using chromatography such as gel permeationchromatography (GPC). The molecular weight of the block copolymer andproperties obtained are dependent upon the molecular weight of each ofthe polymers or polymeric blocks.

The term “cure” or “curing” refers to the hardening or toughening of apolymer material by cross-linking of the polymer chains in the polymer.Such process may be performed by various methods, including by heat,light (UV or visible), radiation, electron beams or by adding certainchemical additives. In certain curing procedures, the additive may beactivated with UV radiation resulting in a UV curing process.

The term “homopolymer” means a polymer that are formed by the reactionstarting with the same monomer. Homopolymers may include additionpolymers that are polymers or macromolecules that are formed by theaddition reaction of olefins, acetylenes, aldehydes or other compoundshaving an unsaturated bond or functional group. Representativehomopolymers from monomers include polyethylene from ethylene,poly(vinyl chloride) from vinyl chloride, polyacrylonitrile fromacrylonitrile, polystyrene from styrene etc.

The term “monomer” means any substance or molecule that can be convertedor made into a polymer. Examples of such monomers may include ethylene,styrene and acrylonitrile. Monomers may also refer to dimers or trimers,if for example, the dimers or trimers can also undergo furtherpolymerization.

“Optionally substituted” means a group, such as an alkyl group, an arylgroup, a heteroaryl group, as disclosed herein, may be substituted byone or more substituents selected from halogen (—F, —Cl, —Br— or —I),—OH, —SH, —SiH₂OH, —NH₂, —NO₂, —CH₃, —CF₃, —OCH₃ and —OCF₃. For example,an optionally substituted or substituted benzyl group substituted with 1substituent selected from the group consisting of halogen (—F, —Cl, —Br—or —I), —OH, —SH, —SiH₂OH, —NH₂, —NO₂, —CO₂H, —SO₄H, —SO₃H, —PO₄H₂, —NH₃⁺, —CH₃, —CF₃, —OCH₃ and —OCF₃.

The term “polymer” means a molecule having a structure that is composedof multiple repeating units, and may refer to a substance or moleculewith high molecular weight. Representative of such polymers may includelinear polymers comprising a long chain of skeletal atoms to which areattached substituents or substituent groups; branched polymers that maybe linear polymers with branches of the same or similar basic structureas the main chain; or cross-linked or network polymers where chemicallinkages are present between the chains of the polymers. The polymers orcopolymers may be random copolymers, alternating copolymers (e.g.,regular alternating A and B monomers), periodic copolymers, statisticalcopolymers or block copolymers.

The term “random” polymers or copolymers are polymers in which themonomer units are incorporated into the chain wherein there can existvarious combinations of ordering including block polymer units where,for example, either the first monomeric unit or second monomeric unit(or third unit, fourth unit etc . . . , as provided herein) or bothunits may be repeated and are adjacent to one another. “Alternating”first monomeric and second monomeric copolymers are those in which thefirst monomeric and second monomeric units occur in repeating alternatesequences on the polymer chain in atactic structures (such as isotacticor syndiotactic) or in combinations of the general formula as describedherein, wherein x and y are integers from 1 to 10,000. The term“substantially random” as used herein in reference to the first andsecond monomeric units form a copolymer where the distribution of themonomers or monomeric units of the copolymer may be described by theBernoulli statistical model or by a first or second order Markovianstatistical model, as described by J. C. Randall in Polymer SequenceDetermination, Carbon-13 NMR Method. Academic Press NY, 1977, pp. 71-78.The composition (of monomer) distribution of the copolymer can also bedetermined using ¹³C NMR analysis using the methods described in U.S.Pat. Nos. 5,292,845; 5,089,321 and by J. C. Randall, Rev. Macromol.Chem. Phys. C29, pp. 201-317 (1989).

In one embodiment, the present application disclosescationic or amphilicionic copolymer-containing heterocycles and heterocyclic salts such aspyridines and substituted pyridines, pyridinium salts, substitutedpyridinium salts, imidazoles and substituted imidazoles, imidazoliumsalts and substituted imidazolium salts, epoxides, glycidol derivatives,hydroxy aromatics, hydroxy phenols, polyhydroxy phenols, catechol andsubstituted catechol monomers which can undergo multiple continuousphase inversion in saline water and may be solidified into an adhesivesuch as a wet adhesive or wet glue. In another embodiment, there isprovided the heterocyclic salts in combination with imidazoles andsubstituted imidazoles, imidazolium salts and substituted imidazoliumsalts, epoxides, glycidol derivatives, hydroxy aromatics, hydroxyphenols, polyhydroxy phenols, catechol and substituted catecholmonomers. These ionic polymer glues can adhere and adsorb onto surfacesof biological tissues, bones, hydrogels, plastics, metals, ceramicsand/or the interfaces between them through a combination ofelectrostatic, hydrophobic, chelating interactions and hydrogen bonding.Lee, B. P.; Messersmith, P. B.; Israelachvili, J. N.; Waite, J. H.,Mussel-Inspired Adhesives and Coatings. Annu Rev Mater Res, 2011, 41,99-132. The bonding strength of these ionic polymer glue can be furtherenhanced through secondary crosslinking with another functional group,for example, by oxidative crosslinking of a functional group, such ascatechol, cationic/anionic/radical polymerization of epoxides,acrylates, methacrylates; coupling/crosslinking of epoxides, arylates,methacrylates, aldehydes, N-succinimidyl group, etc., and at differentpH, such as at pH>6 conditions.

Some embodiments of the current invention are discussed in detail below.In describing embodiments, specific terminology is employed for the sakeof clarity. However, the invention is not intended to be limited to thespecific terminology so selected. A person skilled in the relevant artwill recognize that other equivalent components can be employed andother methods developed without departing from the broad concepts of thecurrent invention. All references cited in this specification, includingthe Background, Detailed Description sections and Examples, areincorporated by reference into this disclosure as if each had beenindividually incorporated.

Some embodiments in the present application are directed to polymers,such as ionic polymers, that may be used under moist or wet conditions,such as an underwater glue. In one embodiment, the underwater adhesive(wet or bio-glue) is based anionic copolymers containing (1)nitrogen-containing heterocyclic cationic functional residues such asimidazolium groups and pyridinium groups, that are selected from thegroup consisting of an ammonium, quinolinium, isoquinolinium,phenathridinium, phenanthrolinium, pyrimidinium, benzothoazolinium,benzothiadiazolinium, purinium, pyrazinium or acridinium and (2)coupling residues such as di, tri-, tetra- and penta-hydroxy benzene,polycyclic hydrocarbons (e.g., naphthalene, anthracene, etc.), aryls,heteroaryl, N-succinimidyl, indole and imidazole moieties and theirderivatives, that may form bonds, such as hydrogen bonds, covalent bondsand/or attachments on to a material surface and/or form crosslinkednetworks such as aldehydes, mono-, di- or poly-acrylates andmethacrylates, di, tri-, tetra- and penta-hydroxy benzene, polycyclichydrocarbons (e.g., naphthalene, anthracene, etc.), aryls, heteroaryl,N-succinimidyl, indole and imidazole moieties and their derivatives.

In one variation, the ionic copolymer may be based on any polymerbackbones such as polystyrene, polyacrylate, polymethacrylate,polyester, polyether from any vinyl, acrylate and/or methacrylateco-monomers.

In one embodiment, the disclosed polymer contains aryl derivatives, suchas benzyl or phenyl derivatives, attached to the pyridine andimidazolium groups through methylene spacer groups. The polymer glue issoluble in water and forms stable aqueous solution. When the aqueoussolution of ionic polymer glue is applied to substrates submerged insaline water (salt concentration: 0.1˜2 M, pH 1˜12 or isotonic), thepolymer can undergo liquid-to-solid phase inversions and self-assembleinto viscoelastic underwater glue. The glue may coat surfaces (e.g.biological tissues, hydrogel, plastics, metal, glass, ceramics) insaline water, or glue two surfaces or objects together. The strength ofthe glue can be further enhanced through the oxidative crosslinking ofmonomers, such as catechol monomers, at pH above 5, 6, 7 or pH 8-9.

In one aspect, x, z are monomer molar ratio of the imidazolium andcatechol monomers in the ionic polymer. In some embodiments, the polymerdisclosed in the present application may be used as underwater glue oradhesive coating in saline water. The ionic polymer glue of the presentapplication have strong adhesion/cohesion in saline water. The ionicpolymer glue may adhere to diverse surfaces and self-assembles into aprimer, a coating, a glue or an adhesive layer. In some embodiments, theionic polymer glue of the present application may be applied ontobiological tissues, such as human tissues, including teeth, bones andmedical and dental implants, and other materials, including plastics,ceramics and metals.

In some embodiments, the adhesive polymer or ionic polymer glue of thepresent application may be crosslinked or further cured, as disclosedherein. In one variation, the polymer may be crosslinked with aqueousoxidizing agents, or in an environment or condition where the pH>6.

In some embodiments, the ionic polymer glue of the present applicationmay be used as an adhesive or a bio-glue for surgical intervention,plastic surgery, dental adhesive, bone adhesive, wet glue fortissue-tissue adhesion and bone-tissue adhesion or joints, underwaterglue for bone-tissue joints, adhesive coatings for dental and medicalimplants, or surface primers for mineral fillers used for polymercomposites including dental and bone cements, adhesives, composites orelectronic devices.

General Scheme for The Preparation of Representative polymers:

Experimental

The procedures for the preparation of the homopolymers or copolymers arebased on a related process for the preparation of highly conductive,mesoporous, graphitic nanostructures as described in J. Yuan et al.,Chem. Mater. 2010, 22, 5003-5012.

General Procedure:

The co-monomers (for example protected catechol acrylate and2-diethylaminoethyl acrylate) are mixed in accordance with the desiredmolar ratios for each application, along with a catalyst (for example,0.01 equiv of a radical photoinitiator, e.g., acrylic acid andazobisisobutyronitrile (AIBN)) dissolved in desired solvent such astoluene/THF for non-polar co-monomers or DMF/diglyme/water for polarco-monomers.

In one particular process of using the copolymers, such as polymerscomprising catechol cationic copolymers, the copolymers are preparedfrom a protected catechol acrylate due to the spontaneous autoxidationof the catechol functional group, or the reactions are carried in acidicconditions to generate a reducing environment (pH<5.5) for catechols. Inone method, where the protecting groups are present, thesilyl-protecting groups are later cleaved in an aqueous pH<3 solution atroom temperature.

Visible or UV light curing system: For further crosslinking of acrylateside groups of non-acrylate copolymers (e.g., polyester with acrylateside chains) to enhance cohesion of glues, visible or UV radicalpolymerization are carried out.

Hand peel test: Once each adhesive film is prepared on PET backing andtested by hand. The stickiness or adhesive property of the tapes inwater is stronger than stickiness of 3M Scotch packing tapes in dryambient condition.

1-Vinyl 3-benzylimidazolium Chloride

The title compound was prepared as follows: 30 ml of N-vinylimidazole(331 mmol, 1 equiv.) was added to a dry round bottom flask fitted with arubber septa, stir bar, and argon needle. 100 ml of anhydrous MeCN wasadded to the flask via syringe, and stirred. Once completely dissolved,30 ml of benzyl chloride (339 mmol, 1.02 equiv.) was added and themixture was stirred at 65° C. for 18-24 hours under argon. The mixturewas then cooled to ambient temperature, and volatiles were removed byrotary evaporation under reduced pressure to obtain a viscous oil.Traces of MeCN and excess benzyl chloride were removed by addition ofdiethyl ether to the flask, which was then vigorously swirled then letsettle, and the ether layer was decanted off from the oil. This processof swirling with ether, settling, then decantation, was repeated severaltimes with fresh ether until no further odor of benzyl chloride could bedetected. The last traces of solvent were then removed on high vacuum toobtain the desired compound as a tan froth of bubbles in quantitativeyield (73 grams, 100%).

Poly (1-vinyl 3-benzylimidazolium Chloride, HP-1)

The title compound was prepared as follows: To a dry round bottom flaskfitted with a stir bar, rubber septa, and argon needle was added 43.7grams of the preceding imidazolium salt dissolved in 150 ml of anhydrousDMF. 164 mg of AIBN (azabisisobutryonitrile, 1 mmol, 0.005 equiv.) wasadded as a solid, and the solution was sparged with argon for 10minutes. Once fully sparged, the flask was heated at 85° C. for 3 days,with stirring. The flask was cooled to ambient temperature, and DMF wasremoved by 3 rounds of coevaporation with toluene on a rotaryevaporator. The polymer was purified by dissolving the crude residue ina minimum amount of methanol, and reprecipitation from THF (volumeMeOH:THF=1:10), where the solid was let settle and supernatantdiscarded. This process of reprecipitation was repeated once more.Traces of methanol were removed by stirring the solids with THF, lettingsettle then decanting off the THF. This process was repeated,substituting hexanes for THF, where after decantation the solids weretransferred by spatula to a round bottom flask, and traces of solventwere removed under high-vacuum to afford pure polymer.

Synthesis of Homopolymer (HP-2)

Into a 50 mL flask equipped with a magnetic stir bar under nitrogen isadded the monomer 4-vinyl-1-benzylpyridinium chloride (M3, 5 g). Themonomer is dissolved in 50 mL of DMF. Azobisisobutyronitrile (AIBN)initiator (100 mg) was added into the solution. The solution is thenstirred at 90° C. for 20 h. The mixture is cooled to room temperature.Polymer is then precipitated and dried as described in the aboveprocedure. About 5 g of HP-2 is obtained after the purification.

Synthesis of Copolymer, P2

Both monomers M1 and M2 are prepared according to literature methods.See for example, J. Yuan et al., Chem. Mater. 2010, 22, 5003-5012.1-Vinyl-3-benzyl imidazolium chloride (monomer M1, 1 g) and silylprotected catechol acrylate derivative (monomer M2, 0.3 g) are added toa 250 mL 3-N RBF with a magnetic stir bar under nitrogen. The monomersare dissolved in N,N-dimethylformamide (DMF, 10 mL) and stirred at roomtemperature for about 15 minutes. Azobisisobutyronitrile (AIBN)initiator (13 mg) is added into the solution mixture, and the reactionmixture is stirred and heated to 80° C. for 24 h (FIG. 1). After thereaction is completed, the solution is transferred to a 500 mL RBF.Diethyl ether (150 mL) is added to the stirred reaction mixture toprecipitate out the crude polymer product, P1.

The resulting mixture with the solid precipitate is stirred at roomtemperature for 15 mins. and DMF (10 mL) is added to re-dissolve thesolids. To the stirred mixture is slowly added diethyl ether (150 mL) tore-precipitate the polymer. Unreacted monomers are dissolved in thediethyl ether and are removed from the product.

The precipitated polymer is filtered with a Buchi filter funnel usingWhatman paper, and the solid polymer is washed with 30 mL diethyl etherand air dried for about 1 hour. The dried polymer is transferred to a250 mL RBF and water (10 mL) is added with stirring to dissolve thepolymer. To the stirred aqueous solution of the polymer at roomtemperature is added 50 mL of aqueous HCl (pH=2, 0.01 M HCl prepared bydissolving 1 mL 0.5 M HCl (Sigma Aldrich) in 49 mL DI water) and stirredfor 2 h, and dialyzed thoroughly as follows. The P1 polymer solution isadded into dialysis tube (molecular weight cutoff: 1000), and isdialyzed against DI water (1 L) for 72 h, during which the water isexchanged with fresh DI water for 5 times. The purified polymer P1 isobtained after freeze drying as follows. P1 polymer solution is freezedat −30° C. and subsequently dried under vacuum (300 Pa pressure) for 24h.

Synthesis of Copolymer P3 and Epoxy Curing to Form Copolymer P4

wherein: x and y define the block polymer and are integer greater than1; and R and R′ are each independently H, C₁-C₆alkyl, —CH₂C₆H₅ whereinthe alkyl and the C₆H₅ are optionally substituted by 1 or 2 substituentsselected from the group consisting of halogen (—F, —Cl, —Br— or —I),—OH, —SH, —SiH₂OH, —NH₂, —NO₂, —CH₃, —CF₃, —OCH₃ and —OCF₃.

FIG. 2. Synthesis of Copolymer P3 and Epoxy Curing to Form P4 Synthesisof Copolymer P3

Both monomers M1 and M3 are prepared according to literature methods.See J. Yuan et al., Chem. Mater. 2010, 22, 5003-5012. 1-Vinyl-3-benzylimidazolium chloride (monomer M1, 1 g) and glycidyl vinyl acetate(monomer M3, 0.2 g) are added to a 250 mL 3-N RBF with a magnetic stirbar under nitrogen. The monomers are dissolved in N,N-dimethylformamide(DMF, 10 mL) and stirred at room temperature for about 15 minutes.Azobisisobutyronitrile (AIBN) initiator (13 mg) is added into thesolution mixture, and the reaction mixture is stirred and heated to 80°C. for 24 h (FIG. 2). After the reaction is complete, the solution istransferred to a 500 mL RBF. Diethyl ether (150 mL) is added to thestirred reaction mixture to precipitate out the crude polymer product,P3. The resulting mixture with the solid precipitate is stirred at roomtemperature for 15 mins and DMF (10 mL) is added to re-dissolve thesolids. To the stirred mixture is slowly added diethyl ether (150 mL) tore-precipitate the polymer. Unreacted monomers are dissolved in thediethyl ether and removed from product.

The precipitated polymer is filtered with a Buchi filter funnel usingWhatman paper, and the solid polymer is washed with 30 mL diethyl etherand air dried for about 1 hour. The purified polymer P3 is obtainedafter freeze drying as follows. P3 polymer solution is freezed at −30°C. and subsequently dried under vacuum (300 Pa pressure) for 24 h.

General Process:

A process for further crosslinking or curing process between the polymeror copolymer functional groups in the polymer chain can also effectedwhen the polymer comprises certain crosslinkable or curable functionalgroups or residues. The crosslinking or curing process may provide asignificantly stronger adhesive when compared to the similar polymericadhesive composition without the additional crosslinking or curing step(e.g., P3 to P4). Such crosslinkable or curable functional groupincludes, for example, a vinyl group, an acrylate, an epoxide, aglycidyl, a hydroxy aryl, polyhydroxy aryl such as a catechol group.

In one embodiment, when the curable group is a hydroxy aryl group, suchas a catechol group, curing of the polymer may be performed by changingthe pH of the aqueous formulation comprising the polymer to a differentpH, such as a more basic pH. For example, the polymer formulation may becontacted with water or an aqueous solution at a pH of about pH of 5,pH>5, pH>5.5, pH>6, pH>6.5, pH>7, pH>7.5, pH>8, pH>8.5, pH>9 or higher.

In another embodiment of the process, the materials or the surface ofthe materials comprising the adhesive may be first contacted or immersedin water or in an aqueous solution, and then the pH of the resultingmixture or composition may be increased to the desired pH, depending onthe nature of the polymer, the functional group and the nature of thematerials being glued together. Without being bound by the proposedmechanism of action disclosed herein, it is believed that the polymer orthe functional groups, such as a hydroxy aryl group, undergo a curing orcrosslinking process by way of an auto-oxidative crosslinking process ormay be initiated by a metal ion(s) via coordination chemistry; to form asignificantly stronger adhesive when compared to the use of the adhesivewithout a curing step. In another embodiment where the polymer comprisesa functional group or residue such as an acrylate, a methacrylate or asubstituted acrylate, the polymer may be crosslinked via visible lightor UV light via photoinitiated polymerization.

In another embodiment, when the polymer comprises an epoxy group, suchas an epoxide or a glycidyl group, the curing step may be performedusing an a reagent, such as an amine. Such an amine may be a di- ortri-amine based epoxy curing agent. Amines that may be used foramine-based epoxy curing includes aliphatic amines such as diethylamine(DEA), methylamine (MA), dimethylamine (DMA), cycloaliphatic amines suchas cyclohexylamine (CHA) and cyclohexylmethylamine (CHMA), and aromaticamines such as aniline (AA) and methylaniline (MAA). Such a curingprocess is similar to that of the method for curing epoxy resin, wherethe adhesive maybe prepared or mixed and cured immediately beforeapplying the adhesive to attach two surfaces. In one method, the driedpolymer is transferred to a 250 mL RBF and water (10 mL) is added withstirring to dissolve the polymer. To the stirred aqueous solution of thepolymer at room temperature is added diethylamine (DEA) and allowed tocure.

Performance of Adhesive Compositions with Different Materials:

Preparation of the Adhesive Composition:

1 g of the homopolymeror the copolymer was added into a 50 mL RBF with amagnetic stirrer. 10 mLof water was added to the homopolymer orcopolymer and the resulting mixture was stirred for 15 minutes to form amilky white, relatively viscous adhesive composition. The adhesionexperiments described below may employ the polymer adhesive composition.

For the copolymers that are functionalized with extra crosslinkableresidues, optionally, there is a second step of curing of the adhesivecomposition that may be performed to increase or enhance the bondingperformance. For example, in the case of the preparation of copolymerswith catechol functional groups (i.e., 3,4-dihydroxyphenyl-), acatechol-mediated auto-oxidation process may be performed.

Accordingly, in addition to joining two test strips of the same ordifferent material composition, the strips (or materials) may beimmersed in water, at a pH of about 5, pH>5, pH>5.5, pH>6, pH>7, pH>8,pH>9, or pH range of 8-9, the polymer undergoes further curing orcrosslinking to form a stronger adhesive. Under certain conditions, thecatechol or other hydroxy benzyl or hydroxy aryl groups may undergoauto-oxidative crosslinking above neutral pH, such as pH>7.

Depending on the type or the nature of the functional groups of thepolymers as described herein, the curing step may also be performed bycrosslinking mechanism or chemistry. For example, where the polymercomprises a hydroxyphenyl group or dihydroxyphenyl group such as acatechol group, the crosslinking process may be initiated by a metalion(s) by way of coordination chemistry. The pH of the solution may belower than pH 5.5, the concentration should be considered with respectto solubility, stoichiometry, and the nature of the metal ion may affectthe crosslinking process.

The adhesive may also be soluble in pure water or in the presence ofsaline or a saline solution. For example, the salt solution may compriseof a single salt or a mixture of salts, including NaBr, NaCl, NaI, LiBr,LiCl and LiI. In one particular aspect, the higher salt concentration(body fluid or sea water) in the applied media will cause a dryingeffect of the polymer when polymer solution in pure water or aqueoussalt solution at low concentration is applied to surfaces in aqueoussalt solution at higher concentration such as body fluid, salt water orsea water.

Two strips of pork tissues of about 1 inch long, half inch wide andabout ⅛ inch thick are immersed in a saline solution for about 10seconds. While leaving the dermises immersed in the saline solution,approximately 1 mL of the adhesive composition is drawn up into apipette and injected or delivered onto one surface of the first of thetwo tissues to form a milky white layer of adhesive of about 2-3 squarecentimeters on the surface. While still immersed in the saline solution,one surface of the second tissue surface is brought into contact withthe first tissue surface with the layer of adhesive and the two tissuesare lightly pressed together for about 2 seconds, and then released. Theresulting tissues are then glued together in the saline solution.

Two strips of plastics (made of PVC, polyethylene or polyurethane) ofabout 1 inch long, half inch wide and about ¼ inch thick are immersed ina saline solution for about 10 seconds. While leaving the plastic stripsimmersed in the saline solution, approximately 1 mL of the adhesivecomposition is drawn up into a pipette and injected or delivered ontoone surface of the first of the two plastic strips to form a milky whitelayer of adhesive of about 2-3 square centimeters on the surface. Whilestill immersed in the saline solution, one surface of the second plasticstrip is brought into contact with the first plastic strip with thelayer of adhesive and the two plastic strips are pressed together with athumb and index finger for about 2 seconds, and then released. Theresulting two plastic strips are then sealed or glued together.

The glues adhere all the different type of materials and surfacesincluding tissue to tissue, tissue to metal, tissue to plastic, tissueto mineral, mineral to metal, mineral to plastic, metal to metal, metalto plastic, plastic to plastic, mineral to mineral, and among othermaterials in wet conditions including under water. Such materialsinclude tissues, such as human tissues, animal tissues, skin, toothenamel, dentine, metals such as aluminum, stainless steel, copper,brass, glass, plastic, and combinations of these materials.

This solution can also be used as a low tack reusable adhesive (such asPost-It® notes). Such low tack or pressure sensitive adhesives mayexhibit a low level of adhesion when first applied and may removecleanly from a surface. In one aspect, the solution comprise of water,ethanol, NaCl, and the adhesive compound. As an example for preparingthe reusable and sprayable low-tack pressure-sensitive adhesivesolution, the adhesive compound is dissolved in water at 1-30 w/v %concentration, then the solution is diluted with ethanol to 10% to 90%.Saturated NaCl aqueous solution (1-30%) is then added. This solution canbe sprayed on or applied to any surfaces that need to be low tack oranti-slippery under moist or wet conditions.

As another example, M2 can be replaced with vinyl alcohol. Aftercopolymerization, the alcohol side group may be modified to acrylate ormethacrylate by reaction with acryloyl chloride or methacryloyl chloridevia acryl chloride esterification by nucleophilic addition-eliminationwith alcohol. The substituted acrylate or methacrylate residues can becrosslinked via radical polymerizations.

While the foregoing description describes specific embodiments, thosewith ordinary skill in the art will appreciate that variousmodifications and alternatives can be developed. Accordingly, theparticular embodiments described above are meant to be illustrativeonly, and not to limit the scope of the invention, which is to be giventhe full breadth of the appended claims, and any and all equivalentsthereof.

What is claimed: 1.-31. (canceled)
 32. A method for sealing a firstobject having a surface to a second object having surface, the methodcomprising: 1) applying an adhesive to the surface of the first object;2) contacting the surface of the first object comprising the adhesivewith the surface of the second object for a sufficient period of timeuntil the first and second object forms a seal; wherein the adhesive isan adhesive composition comprising a polymer of the formula A or B:

wherein: each m and n is independently 100 to 1,000,000; each a, b, sand t is independently 0, 1 or 2; each L¹, L², L³ and L⁴ isindependently absent or is independently selected from —CH₂—, —O—, —S—,—(CH₂)₁₋₂—, —CH(CH₂—)₂, —C(O)O—, —C(O)OCH₂—, —CH₂C(O)O—, —CH₂C(O)NH—,—C(O)NHCH₂—, —C(O)NH— and —NR′— where R′ is selected from H, —CH₃,—CH₂CH₃ and —CH₂C₆H₅ or substituted benzyl, or a bond; each A, B, M andN is independently absent or is independently selected from the groupconsisting of an aryl, substituted aryl, heteroaryl, substitutedheteroaryl, heteroarylammonium X⁻ and substituted heteroarylammonium X⁻,wherein each X⁻ is independently a counter anion selected from the groupconsisting of Cl⁻, Br⁻, I⁻, —SO₄ ⁻² and —PO₄ ⁻³; provided that not allof L¹, L², L³ and L⁴ and A, B, M and N are absent.
 33. The method ofclaim 32, wherein the adhesive comprises of the formulae A¹, A², A³, A⁴,A⁵, A⁶, A⁷, A⁸, A⁹, A¹⁰, A¹¹, A¹², A¹³ and A¹⁴:

wherein: each n is independently 100 to 1,000,000; each L¹ and L³ isindependently selected from a bond, —CH₂—, —O—, —S—, —C(O)O—,—C(O)OCH₂—, —CH₂C(O)O—, —CH₂C(O)NH—, —C(O)NHCH₂—, —C(O)NH— and —NR′—where R′ is selected from H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅ or substitutedbenzyl; each R and R¹ is independently H or is selected from the groupconsisting of F, Cl, Br, I, —OH, —SiH₂OH, —NO₂, —CH₃, —CO₂H, —SO₄H,—SO₃H, —PO₄H₂, —PO₃H₂, —NH₃ ⁺, —CH₂C₆H₅, -3,4-dihydroxyphenyl, a curablegroup, —CH₂-3,4-dihydroxyphenyl, —NR′R″ where R′ and R″ are eachindependently selected from H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅ or substitutedbenzyl; each R³ is independently H or is selected from the groupconsisting of —CH₃, —CH₂CH₃, a curable group and —CH₂C₆H₅ where the C₆H₅group is optionally substituted with 1 substituent selected from thegroup consisting of halogen (—F, —Cl, —Br— or —I), —OH, —SH, —SiH₂OH,—NH₂, —NO₂, —CO₂H, —SO₄H, —SO₃H, —PO₄H₂, —PO₃H₂, —NH₃ ⁺, —CH₃, —CF₃,—OCH₃ and —OCF₃; and each X⁻ is independently a counter anion selectedfrom Cl⁻, Br⁻, I⁻, —SO₄ ⁻², —PO₄ ⁻³ and CH₃CO₂. each X⁻ is independentlya counter anion selected from the group consisting of Cl⁻, Br⁻, I⁻, —SO₄⁻² and —PO₄ ⁻³.
 34. The method of claim 32, wherein the adhesivecomprises of the formulae B¹, B², B³, B⁴, B⁵ and B⁶:

wherein: each m and n is independently 100 to 1,000,000; each L¹ and L³is independently selected from a bond, —CH₂—, —O—, —S—, —C(O)O—,—C(O)OCH₂—, —CH₂C(O)O—, —CH₂C(O)NH—, —C(O)NHCH₂—, —C(O)NH— and —NR′—where R′ is selected from H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅ or substitutedbenzyl; each R and R¹ is independently H or is selected from the groupconsisting of F, Cl, Br, I, —CF₃, —OH, —SiH₂OH, —NO₂, —CO₂H, —SO₄H,—SO₃H, —PO₄H₂, —PO₃H₂, —NH₃ ⁺, —CH₃, —CH₂C₆H₅, -3,4-dihydroxyphenyl,—CH₂-3,4-dihydroxyphenyl, a curable group, —NR′R″ where R′ and R″ areeach independently selected from H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅ orsubstituted benzyl; each R³ is independently H or is selected from thegroup consisting of —CO₂H, —SO₄H, —SO₃H, —PO₄H₂, —PO₃H₂, —NH₃ ⁺, —CH₃,—CH₂CH₃, —CH₂C₆H₅ or substituted benzyl, and a curable group; and eachX⁻ is independently a counter anion selected from the group consistingof Cl⁻, Br⁻, I⁻, —SO₄ ⁻² and —PO₄ ⁻³.
 35. The method of claim 32,wherein at least one of (A), (B), (M) and (N) is independently selectedfrom the group consisting of the formulae:-L¹-COOH, -L¹-SO₄H, -L¹-SO₃H, -L¹-PO₄H₂, -L¹-PO₃H₂ and L¹-NH₃ ⁺; and-L³-COOH, -L³-SO₄H, -L³-SO₃H, -L³-PO₄H₂, -L³-PO₃H₂ and L³-NH₃ ⁺; whereineach L¹ and L³ is independently selected from a bond, —CH₂—, —O—, —S—and —NR′— where R′ is selected from H, —CH₃, —CH₂CH₃ and —CH₂C₆H₅. 36.The method of claim 32, wherein each of (B) and (N) independentlycomprises a derivative of the formulae:


37. The method of claim 32, wherein each of (B) and (N) is independentlyselected from the group consisting of the formulae:


38. The method of claim 32, wherein at least one of (A) and (M) isindependently selected from the group consisting of the formulae:


39. The method of claim 32, wherein the adhesive is further cured. 40.The method of claim 32, wherein the first object is independentlyselected from the group consisting of a dermis, metal, a metal oxide, amineral, mica, silicon, glass, calcium, enamel, bone, steel, toothenamel, tooth dentin, hydroxylapatite, kaolin and zirconia; and thesecond object is selected from the group consisting of a tissue, dermis,metal, a metal oxide, a mineral, mica, silicon, glass, calcium, enamel,bone, steel, tooth enamel, tooth dentin, hydroxylapatite, kaolin andzirconia.
 41. The method of claim 32, wherein the first object is dermisand the second object is selected from the group consisting of a metal,a metal oxide, a mineral, mica, silicon, glass, calcium, enamel, bone,steel, tooth enamel, tooth dentin, hydroxylapatite, kaolin and zirconia.42. The method of claim 32, wherein the adhesive process is performed inwater.
 43. The method of claim 43, wherein the method further comprisesthe addition of saline, salt or a mixture of salt to increase thesalinity.
 44. The method of claim 32, wherein the method provides areusable or reversible low tack pressure sensitive adhesive or low tackadhesive or anti-slippery coating wherein the process comprises: (1)dissolving the adhesive comprising a polymer of the formula A or B:

wherein: each m, n and o is independently 100 to 1,000,000; each a, b,s, t, x and y is independently 0, 1 or 2; each L¹, L², L³ and L⁴ isindependently absent or is independently selected from —CH₂—, —O—, —S—,—(CH₂)₁₋₂—, —CH(CH₂—)₂, —C(O)O—, —C(O)OCH₂—, —CH₂C(O)O—, —CH₂C(O)NH—,—C(O)NHCH₂—, —C(O)NH— and —NR′— where R′ is selected from H, —CH₃,—CH₂CH₃ and —CH₂C₆H₅ or substituted benzyl, or a bond; each (A), (B),(M) and (N) is independently absent or is independently selected fromthe group consisting of an aryl, substituted aryl, heteroaryl,substituted heteroaryl, heteroarylammonium X⁻ and substitutedheteroarylammonium X⁻, wherein each X⁻ is independently a counter anionselected from the group consisting of Cl⁻, Br⁻, I⁻, —SO₄ ⁻² and —PO₄ ⁻³;provided that not all of L¹, L², L³ and L⁴ and (A), (B), (M) and (N) areabsent, in water to form an aqueous solution of the adhesive; (2)diluting the aqueous solution of the adhesive with ethanol; (3) addingsaturated NaCl aqueous solution to the aqueous ethanolic solution; and(4) spraying or coating the aqueous ethanolic solution on a substrateand air drying the solution.
 45. The method of claim 44, wherein thesalt is selected from the group consisting of NaBr, NaCl, NaI, LiBr,LiCl and LiI.